CN101161715A - Fire-resistant rubber composition, fire-resistant covering material composed of the composition and fire-resistant covering processing method using the same - Google Patents

Fire-resistant rubber composition, fire-resistant covering material composed of the composition and fire-resistant covering processing method using the same Download PDF

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CN101161715A
CN101161715A CNA2007101811812A CN200710181181A CN101161715A CN 101161715 A CN101161715 A CN 101161715A CN A2007101811812 A CNA2007101811812 A CN A2007101811812A CN 200710181181 A CN200710181181 A CN 200710181181A CN 101161715 A CN101161715 A CN 101161715A
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fire
mass parts
resistant covering
rubber composition
covering material
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CN101161715B (en
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齐藤清高
佐藤克彦
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Crk K K
Denka Co Ltd
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Crk K K
Denki Kagaku Kogyo KK
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Abstract

The present invention provides a fire-resistant rubber composition, forming body can keep enough shape stability even exposed in very hot condition, also excellent operation efficiency can be applied to fire-resistant material formed from the fire-resistant composition. The present invention provides an unvulcanized fire-resistant rubber composition, in 100 mass ratio of base rubber components composed of 30 to 50 mass ratio of liquid rubber, 50 to 70 mass ratio of butyl rubber, 10 to 60 mass ratio of bonding agent, 10 to 100 mass ratio of heat expansion graphite, 50 to 170 mass ratio of aluminum phosphorous acid, 50 to 170 mass ratio of inorganic filler, 0.1 to 10 mass ratio of vulcanizing agent and 0.1 to 10 mass ratio of vulcanizing accelerator are contained for mixing at 60 to 100 Degrees. In addition, fire-resistant cover material shaped by the fire-resistant rubber composition and fire-resistant cover process method using the same are provided.

Description

Flame resistance rubber composition, the fire-resistant covering material that constitutes by this flame resistance rubber composition and the fire-resistant covering treatment process of having used this fire-resistant covering material
Technical field
The present invention relates to the fire-resistant covering material of Steel Skeleton or run through flame resistance rubber composition used in the seam sealer etc. of portion at spacer body, the fire-resistant covering material that constitutes by this flame resistance rubber composition and the fire-resistant covering treatment process of having used this fire-resistant covering material.More particularly, be exposed under the extremely hot situation even relate to, foam also can keep enough shape stabilities, and the good flame resistance rubber composition of constructing operation; The fire-resistant covering material that constitutes by this flame resistance rubber composition; And used fire-resistant covering treatment process of this fire-resistant covering material etc.
Background technology
Because Steel Skeleton as a rule its temperature reaches about more than 550 ℃ the time, intensity will reduce sharp, therefore when presence of fire in the buildings of Steel Skeletons such as multi-storey building or sky parking, will produce the danger of collapsing.Thus, the surface of the Steel Skeleton that needs protection when fire makes temperature be lower than described 550 ℃, with this end in view, considers various fire-resistant covering factures.
As used in the past fire-resistant covering facture, have the Steel Skeleton surface with the method for mineral-type refractory materialss such as calcium silicate board or plasterboard covering, with the method for inorganic fibers such as asbestos to the Steel Skeleton injection.But,, then, effective inadequately in construction because the thickness of cover part becomes big, and therefore the volume of the Steel Skeleton integral body that is capped will become greatly if utilize the covering of calcium silicate board or plasterboard etc.In addition, if the method for limpet asbestos etc. then produces inequality easily in thickness, in the resistivity against fire of each one of Steel Skeleton, produce deviation easily.In addition, the droplet that when construction, disperses easily, or in maintenance, need for a long time, thereby be not effective means.
In addition, in fire-resistant covering was in recent years handled, not only merely requiring had material self to be difficult to the incendiary fire performance, but also requires to have the function that spreads that prevents flame, i.e. fire resistance.So, adopt and used the fire-resistant covering facture of fire prevention with expanding material.So-called fire prevention is meant with expanding material, in case when presence of fire, be exposed to extremely hot in, will moment ground expand (thermal expansion), form the material of foam insulation (foam).Utilize this foam, the flame that intention spreads can be stopped up and blocked in the gap of fireproof brickwork and power cable etc., or performance protects the surface of Steel Skeleton to avoid the effect of heat insulation of temperatures involved.
As this kind fire prevention expanding material, used the resistivity against fire composition that in rubber constituent, has cooperated thermally expandable graphite or inorganics etc. in the past.But, rubber constituent or thermally expandable graphite are owing to himself have the character of burning or heat fusing in itself, therefore how can prevent the hot melt of the foam of thermal expansion for a long time, perhaps how can inorganic components be come off and it is kept, just become the very important key element of aspect of performance at decision resistivity against fire composition.
So, the applicant is in patent documentation 1, even the protection expanding material of the shape that can keep for a long time stipulating as after thermal expansion, also not causing hot melt, announced following fire prevention seam sealer, promptly, in rubber constituent, cooperate thermoplastic elastomer, added expansile graphite, boric acid and inorganic filling material.But,,,, need utilize caking agent to be attached on the Steel Skeleton etc. therefore in fire-resistant covering material use because fire prevention does not have binding property with seam sealer self though this fire prevention is good aspect the shape stability that is exposed to when extremely hot with seam sealer.
On the other hand, as having fusible resistivity against fire composition, announced to have fusible rubber combination, phosphorus compound, be neutralized the resistivity against fire resin combination that thermally expandable graphite, moisture inorganics and the metal carbonate handled have mixed in the patent documentation 2.Having excellent moldability of this resistivity against fire resin combination, and can bring into play sufficient fire performance.
[patent documentation 1] spy opens the 2006-87819 communique
[patent documentation 2] spy opens the 2000-34365 communique
Therefore the resistivity against fire resin combination of being announced in the patent documentation 2 does not need caking agent owing to have binding property when being attached on Steel Skeleton or the wall as fire-resistant covering material.But, because the bounding force that only utilizes the resistivity against fire resin combination to be had, cementability is not enough, therefore after being attached at fire-resistant covering material on Steel Skeleton or the wall, often to utilize fixedly surfacing such as non-woven fabrics, wire netting, stupalith and it is strengthened (with reference to 0051 section of patent documentation 2) such as nail or pin, bolt etc. from the outside.It also is in order to prevent to be exposed to peeling off, coming off and essential operation of fire-resistant covering material when extremely hot after construction that this kind strengthened fixing, yet owing to be the operation that need spend a lot of time, therefore just becomes the essential factor that reduces operating efficiency widely.
Summary of the invention
So, main purpose of the present invention is, even provide a kind of under situation about being exposed in extremely hot, foam also can keep the flame resistance rubber composition of enough shape stability, be can to its shaping and fire-resistant covering material give the flame resistance rubber composition of good operating efficiency.
In order to solve described problem, the inventor etc. further investigate repeatedly, consequently, flame resistance rubber composition as the enough shape stabilities of maintenance, and as can to its shaping and fire-resistant covering material give good " binding property " in when construction, the flame resistance rubber composition of firm " stationarity " after the construction, formed following flame resistance rubber composition.
Promptly, the present application at first provides a kind of unvulcanized flame resistance rubber composition, with respect to basic rubber constituent 100 mass parts that constitute by aqueous rubber 30~50 mass parts, isoprene-isobutylene rubber 50~70 mass parts, contain tackiness agent 10~60 mass parts, thermally expandable graphite 10~100 mass parts, aluminum phosphite 50~170 mass parts, inorganic filler 50~170 mass parts, vulcanizing agent 0.1~10 mass parts, vulcanization accelerator 0.1~10 mass parts, described unvulcanized flame resistance rubber composition is used at 60~100 ℃ mixing down.
Here, among the present invention, the what is called of fire-resistant covering material " binding property " is meant following character, promptly, with fire-resistant covering material in the surface construction of base materials such as Steel Skeleton, fire-resistant covering material is bonding to substrate surface based on the bounding force that self had, and is held.In addition, this adhering state is called simply " bonding " or " tacky state ".
The fire-resistant covering of tacky state is handled material owing to kept flexibility, even therefore temporarily after substrate surface attaches, can also divest once more.
Different with it, the what is called of fire-resistant covering material " stationarity " is meant following character, that is, fire-resistant covering is handled material and increased hardness because of " virgin sulfur voltinism " described later, to firmly fixing of substrate surface.In addition, this adhering state is called simply " fixing " or " stationary state ".
The fire-resistant covering of stationary state is handled material owing to having increased hardness, having lost flexibility, therefore can't peel off easily from substrate surface.
And " bonding " is as comprising the term that described " bonding " reaches the notion use of " fixing ".
Below, for each composition of aqueous rubber, isoprene-isobutylene rubber, tackiness agent, thermally expandable graphite, aluminum phosphite, inorganic filler, vulcanizing agent, vulcanization accelerator contained that ratio is specific to be the meaning of described scope, mainly to this flame resistance rubber composition is shaped the good binding property of fire-resistant covering material when giving construction, the firm fixed viewpoint after the construction, be respectively described below.
The basis rubber constituent is mixed isoprene-isobutylene rubber 50~70 mass parts and is formed in aqueous rubber 30~50 mass parts.Under the situation of aqueous rubber less than 30 mass parts, basic rubber constituent becomes (penetration degree is little) really up to the mark, and the processibility of flame resistance rubber composition reduces, and in addition, it is not enough that the binding property of the fire-resistant covering material of gained becomes.In addition, when aqueous rubber surpassed 50 mass parts, then basic rubber constituent became too soft (penetration degree is big), and the fire-resistant covering material of gained becomes and is difficult to dispose, and operability reduces.So, by aqueous rubber and isoprene-isobutylene rubber are formed basic rubber constituent with described extra fine quality than cooperating, just can obtain to possess the flame resistance rubber composition of ideal processibility, and then can obtain at operability good fire-resistant covering material aspect the binding property particularly.
In addition, by tackiness agent being coupled in the basic rubber constituent, just can further improve the binding property of the fire-resistant covering material of gained.The content of tackiness agent is 10~60 mass parts with respect to basic rubber constituent 100 mass parts, preferred 15~40 mass parts.This be because, when being less than 10 mass parts, then the binding property of fire-resistant covering material becomes insufficient, when using when surpassing 60 mass parts, then the intensity of fire-resistant covering material will step-down.
The content of thermally expandable graphite is 10~100 mass parts with respect to basic rubber constituent 100 mass parts, preferred 20~70 mass parts.This be because, when the content of thermally expandable graphite is less than 10 mass parts, then have the situation of not thermal expansion fully of flame resistance rubber composition (or fire-resistant covering material) (the thermal expansion multiplying power is little), when surpassing 100 mass parts, though then the thermal expansion multiplying power of flame resistance rubber composition (or fire-resistant covering material) becomes big, the shape stability of the foam after the thermal expansion reduces.
In addition, the content of aluminum phosphite is 50~170 mass parts with respect to basic rubber constituent 100 mass parts, preferred 50~130 mass parts.This be because, when being less than 50 mass parts, then the shape stability of flame resistance rubber composition (or fire-resistant covering material) becomes insufficient, when surpassing 170 mass parts, then the processibility of flame resistance rubber composition reduces.
The content of inorganic filling material is 50~170 mass parts with respect to basic rubber constituent 100 mass parts, preferred 70~160 mass parts.This be because, when being less than 50 mass parts, then the undercapacity of the foam of flame resistance rubber composition (or fire-resistant covering material) can't be brought into play thermotolerance, flame retardant resistance, when surpassing 170 mass parts, then the processibility of flame resistance rubber composition reduces.
By in basic rubber constituent, with described extra fine quality than cooperating thermally expandable graphite and aluminum phosphite, inorganic filler, just can obtain following flame resistance rubber composition (or with its fire-resistant covering material that has been shaped), promptly, possess ideal thermal expansion multiplying power and processibility, even be exposed to for a long time under the high temperature and thermal expansion, its foam also is difficult to fragilityization, has enough shape stabilities.
Here, the present application people finds, by each composition is descended mixing processing at 60 ℃~100 ℃, the carrying out that suppresses the vulcanization reaction of flame resistance rubber composition, just can under environment, utilize the sulfurations (natural vulcanization) naturally such as radiant heat of sunlight, obtain to possess the unvulcanized flame resistance rubber composition of the characteristic of little by little gaining in strength.
Among the present invention, the sulfuration of this flame resistance rubber composition (or fire-resistant covering material) under the environment of radiant heat of sunlight etc. is called " natural vulcanization ".Utilize this natural vulcanization, the flame resistance rubber composition will little by little increase hardness.
So the refractory process material that is shaped by the flame resistance rubber composition after the described mixing processing has good flexibility and binding property at first, the good binding property in the time of can bringing into play construction.In addition, the construction back utilizes the natural vulcanizations such as radiant heat of sunlight under environment, little by little gain in strength, thus immobilization.
The present application people is for the characteristic optimizing of this kind based on the flame resistance rubber composition (or fire-resistant covering material) of virgin sulfur voltinism, with vulcanizing agent and vulcanization accelerator to contain ratio specific with respect to basic rubber constituent 100 mass parts respectively be the scope of 0.1~10 mass parts.This ratio is the scope of 1~5 mass parts more preferably.This be because, distinguish, when vulcanizing agent and vulcanization accelerator are less than 0.1 mass parts with respect to basic rubber constituent 100 mass parts respectively, then can't bring into play the virgin sulfur voltinism, or the carrying out of natural vulcanization (natural vulcanization speed) is slow excessively, and it is not enough that the intensity of flame resistance rubber composition (or fire-resistant covering material) becomes, when using when surpassing 10 mass parts, then natural vulcanization speed becomes too fast, the poor stability during keeping.
Mixing by the flame resistance rubber composition that each composition such as aqueous rubber, isoprene-isobutylene rubber, tackiness agent, thermally expandable graphite, aluminum phosphite, inorganic filler and vulcanizing agent, vulcanization accelerator are contained with described specific ratios is carried out under 60~100 ℃, will make as described above and have ideal flexibility and fusible fire-resistant covering material.In addition, the fire-resistant covering material that obtains possesses ideal virgin sulfur voltinism, can bring into play the intensity after suitable vulcanization rate and the enough sulfuration.
More particularly, for example use two rotors formula kneading device under 80 ℃ mixing 5 minutes with 40 rev/mins rotating speed, add vulcanizing agent and vulcanization accelerator, then under 100 ℃ mixing 5 minutes with described rotating speed, the penetration degree of having carried out the flame resistance rubber composition after this mixing treatment process is 30~65, becomes the material that possesses the ideal flexibility.
In addition, the sulphidity of the flame resistance rubber composition after having carried out mixing processing under the identical condition is below 5%.
Here, suppose to have carried out under the situation of mixing processing having surpassed under 100 ℃ the temperature, vulcanization reaction can aggravate to carry out in mixing, and the flexibility of the flame resistance rubber composition of gained is brought obstruction, might can't bring into play suitable virgin sulfur voltinism shown below.
That is, the flame resistance rubber composition after the described mixing processing under 50 ℃ of atmosphere through 120 days more than the postcure to 70%, performance ideal virgin sulfur voltinism.
And, the two rotors formula kneading device that can be used for described mixing treatment process is for example so long as can be at the mixing device under the rotating speed of 40 rev/mins of realizations under 80 ℃ to 100 ℃, just can be not particularly limited to use, among the present invention, the mixing capacity of having used the oriyama of M Co., Ltd. system of extensively popularizing now is 3 liters a pressurization kneader (machine name: the DS3-10MWB-S type).
Making under the situation of fire-resistant covering material by flame resistance rubber composition discussed above, with this flame resistance rubber composition after having carried out mixing processing under 60~100 ℃, form processing.At this moment, by the shaping treatment temp is remained on 60~100 ℃, just can keep the sulphidity (below 5%) of the flame resistance rubber composition after the described mixing processing.This be because, when the shaping treatment temp surpassed 100 ℃, then the vulcanization reaction of flame resistance rubber composition will aggravate to carry out, the binding property of the fire-resistant covering material of gained and flexibility reduce, and might can't bring into play suitable virgin sulfur voltinism.In addition, preferably the shaping treatment temp is remained the temperature that is lower than mixing processing.
The fire-resistant covering material that so is shaped is owing to have a good binding property after shaping, therefore with fire-resistant covering material during to the surface construction of base material, fire-resistant covering material will be bonding to substrate surface based on the bounding force that self had, and be held.So, different with fire prevention in the past with expanding material, when on Steel Skeleton, wall etc., attaching, do not need to utilize nail, pin, bolt to wait and strengthen fixedly surfacings such as non-woven fabrics, wire netting, stupalith.In addition, because the fire-resistant covering material of tacky state has been kept flexibility, even therefore temporarily after having carried out the location, also can divest and attaching again once more to attaching on the substrate surface.
In addition, the fire-resistant covering material that is attached on Steel Skeleton or the wall etc. is little by little gained in strength because of natural vulcanization, and the tacky state at the beginning of attaching little by little is changed to stationary state, forms firm covering on the surface of Steel Skeleton or wall.Form the fire-resistant covering material of firm covering like this because the situation of not peeling off easily, coming off, therefore do not need picture fire prevention usefulness expanding material thing in the past, after attaching on Steel Skeleton or the wall etc., utilize nail, pin, bolt etc. to strengthen fixedly surfacings such as non-woven fabrics, wire netting, stupalith from the outside, even under situation about being exposed in extremely hot, also be difficult to peel off, come off.
Fire-resistant covering treatment process of the present invention is to have utilized the method for the characteristic of the fire-resistant covering material of this kind, it is characterized in that, when construction, utilize bounding force that fire-resistant covering material self had to attach and bonding to substrate surface, thereafter, make it to the substrate surface immobilization by the natural vulcanization that utilizes fire-resistant covering material, and obtain firm mulch film.
In this fire-resistant covering treatment process, as mentioned above,, therefore can increase substantially operating efficiency owing to do not need necessary in the past nail, pin, the bolt etc. of utilizing that surfacings such as non-woven fabrics, wire netting, stupalith are strengthened fixing.
In addition, banded or laminar by fire-resistant covering material is made at this moment, just can be attached at more easily on Steel Skeleton or the wall etc., can further improve operating efficiency.
Even flame resistance rubber composition of the present invention is owing to also can keep enough shape stabilities under situation about being exposed in extremely hot, spreading in the time of therefore can suppressing fire effectively, and the firm stationarity after the good binding property in the time of can bringing into play construction owing to the refractory process material that is shaped by this flame resistance rubber composition, the construction, therefore when on Steel Skeleton or wall, attaching, do not need to strengthen fixing, can improve the efficient of fire-resistant covering processing operation significantly.
Embodiment
To describe being used to implement ideal mode of the present invention below.And, below illustrated embodiment be the mode of an example of expression representational embodiment of the present invention, and do not have situation about range reduction of the present invention ground being explained by it.
Aqueous rubber as used among the present invention for example can use polyhutadiene, polyisoprene, polybutene, so long as can give fusible aqueous rubber to flame resistance rubber composition (or fire-resistant covering material), just can be not limited to their ground and adopt.Can with these aqueous rubber mix with isoprene-isobutylene rubber more than a kind or 2 kinds and as basic rubber constituent.
Tackiness agent uses for the binding property that further improves flame resistance rubber composition (or fire-resistant covering material).As tackiness agent, for example can enumerate coumarone-indene resin, resol, terpene-phenolic resin, polyterpene resin, petroleum-type hydrocarbons resin etc.Tackiness agent can use a kind or be used in combination more than 2 kinds.
When in a single day thermally expandable graphite is exposed to temperature above about 220 ℃, more than will thermal expansion to 100 times, can bring into play following effect, promptly, when fire takes place, form firm foam insulation and prevent that the temperature of Steel Skeleton etc. from rising at the covering surfaces of Steel Skeleton etc., in addition, the gap of fireproof brickwork and power cable etc. can be stopped up and prevent the inflow of flame.In thermally expandable graphite, can use following crystalline compounds, that is, the powder of natural graphite, pyrolytic graphite etc. is handled the crystalline compounds that obtains, keeps the graphite laminate structure with strong oxidizers such as mineral acids such as sulfuric acid or nitric acid, concentrated nitric acid or permanganates.And, in the powder of natural graphite, pyrolytic graphite etc., though the various kinds of having carried out depickling processing or neutralizing treatment etc. are arranged, which kind of uses can.About preferred 20~400 orders of the granularity of thermally expandable graphite.This be because, when granularity during less than 400 orders, then the turgidity of thermally expandable graphite is little, can rewarding flame resistance rubber composition (or fire-resistant covering material) situation of thermal expansion fully not when fire, in addition, when granularity during greater than 20 orders, then dispersed variation, the elasticity of flame resistance rubber composition reduces.
Aluminum phosphite uses as the dimensionally stable agent of the type avalanche that is used to prevent the foam after the thermal expansion.For the median size of aluminum phosphite, consider from the viewpoint of dispersiveness, in preferred 1~100 μ m of the measured value of laser diffractometry.
Inorganic filler plays the effect of framework material in flame resistance rubber composition (or fire-resistant covering material), at flame resistance rubber composition (or fire-resistant covering material) in fire after the thermal expansion, can improve the intensity of its foam, or help the increase of thermal capacity and strengthen thermotolerance.As inorganic filler,, for example can enumerate red phosphorus, phosphate metal salt, ammonium polyphosphate class inorganic phosphorous compounds such as (ammonium polyphosphate, melamine-modified ammonium polyphosphates etc.) though be not particularly limited; Metal oxides such as aluminum oxide, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, ferric oxide, stannic oxide, weisspiessglanz, ferrous acid salt; Moisture inorganicss such as calcium hydroxide, magnesium hydroxide, aluminium hydroxide, hydrotalcite; Metal carbonates such as alkaline magnesium carbonate, lime carbonate, magnesiumcarbonate, zinc carbonate, Strontium carbonate powder, barium carbonate; Calcium salts such as calcium sulfate, gypsum fiber, Calucium Silicate powder; Silicon oxide, diatomite, dawsonite, barium sulfate, talcum, clay, mica, montmorillonite, wilkinite, atlapulgite, sepiolite, imogolite (ィ モ go ラ ィ ト), sericite, glass fibre, granulated glass sphere, be sealed with the silica type hollow-particle (バ Le Application) of gas, aluminium nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, be sealed with ash content (ash) hollow-particle of gas, the charcoal powder, various metal powders, potassium titanate, sal epsom, metatitanic acid zirconic acid zinc, aluminium borate, moly-sulfide, silicon carbide, Stainless Steel Fibre, zinc borate, various magnetic powders, the slag staple fibre, flying dust etc.They both can use separately, and also two or more kinds may be used.
Vulcanizing agent and vulcanization accelerator are in order to give the virgin sulfur voltinism to flame resistance rubber composition (or fire-resistant covering material) and to cooperate.Vulcanizing agent just is not particularly limited so long as can vulcanized rubber is crosslinked, yet for example sulphur is arranged, sulphur compounds such as polysulphide; Oxime compounds such as p-quinone dioxime, p,p-dibenzoylquinone dioxime; Organo-peroxide compounds such as tert-butyl hydroperoxide, acetyl peroxide benzylacetone, cumine hydroperoxide etc.The preferred sulphur compounds of vulcanizing agent also can be used in combination this sulphur compounds and the compound beyond it.Vulcanization accelerator is that purpose is used with the sulfuration that promotes vulcanized rubber, be not particularly limited, yet for example can enumerate tetramethyl-thiuram disulfide, thiuram compound such as tetrabutylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylene thiuram tetrasulfide; Thiazole compound such as 2-mercaptobenzothiazole or dibenzothiazyl disulfide; Two thiocarbamate salt compounds such as dimethyl dithiocarbamate zinc, diethyldithio-carbamate zinc di-n-butyl two thiocarbamate zinc; Aldehyde amino benzenes compounds such as butyraldehyde-n aniline; N-cyclohexyl-sulfinyl amine compounds such as 2-[4-morpholinodithio sulfinyl amine; Guanidine compounds such as di-o-tolylguanidine or two adjacent nitrile guanidines; Thiourea such as thiocarbanilide or diethyl thiourea, trimethyl thiourea; Compounds such as zinc white.Vulcanization accelerator not only can use their monomer, also can will be used in combination more than 2 kinds.
Described each composition of aqueous rubber, isoprene-isobutylene rubber, tackiness agent, thermally expandable graphite, aluminum phosphite, inorganic filler, vulcanizing agent, vulcanization accelerator is specificly contained the of the present invention unvulcanized flame resistance rubber composition that ratio has mixed with what the scope of technical scheme put down in writing, possess ideal thermal expansion multiplying power and processibility, even be exposed under the high temperature, its foam also can be brought into play enough shape stabilities.In addition, the penetration degree after mixing under 60~100 ℃ is 30~65, also possesses the ideal flexibility.In addition, this flame resistance rubber composition also possesses ideal virgin sulfur voltinism, can bring into play the intensity behind suitable natural vulcanization speed, the enough natural vulcanization.More particularly, at 60~100 ℃ of sulphidities after down mixing below 5%, thereafter under 50 ℃ the atmosphere through 120 days after, vulcanize to more than 70%.Here, can certainly different temperature and during in evaluation natural vulcanization speed.
In the flame resistance rubber composition, in the scope that does not hinder its effect, can also and use softening agent, tenderizer, protective agent, processing aid, lubricant etc.As the example of effective tenderizer or softening agent for the adjustment of processibility, can enumerate ester plasticizer class, stearic acid or its ester class etc. of treated oils such as paraffin class or naphthenic, Liquid Paraffin or other paraffin class, wax class, phthalic acid or hexanodioic acid class, sebacic acid class or phosphoric acid class etc.
As the device that the flame resistance rubber composition is mixing, known in the past two rotors formula kneading device is arranged, for example Banbury mixer, kneader agitator etc.In the fire-resistant covering material that is shaped by the flame resistance rubber composition, methods such as in the past drawing, extrusion molding, calendaring molding are arranged.Here, when the temperature in mixing operation and the forming process surpassed 100 ℃, then the sulfuration of flame resistance rubber composition will be carried out, and the binding property of the fire-resistant covering material of gained and flexibility might reduce.So, the temperature of mixing forming process need be remained on below 100 ℃, so just sulphidity can be maintained below 5%, obtain possessing binding property and flexibility, the fire-resistant covering material of performance ideal virgin sulfur voltinism.And the lower limit of the temperature of mixing shaping is the temperature that kneading device temperature that can turn round or forming process can be shaped, and for example is respectively 60 ℃.In addition, carry out in order not make sulfuration, the forming temperature of forming process preferably is lower than melting temperature.
[embodiment]
Below will utilize embodiment and comparative example that the present invention is more specifically illustrated, however these embodiment and non-limiting example of the present invention.And the part in the following description is based on quality criteria.Used material is respectively material shown below among the embodiment.
(1) aqueous rubber: polybutene; BP Japan (strain) system, " H-300 "
(2) isoprene-isobutylene rubber: JSR (strain) system, " Butyl268 "
(3) tackiness agent: terpene resin; Yasuhara Chemical (strain) system, " YS Resin PX-100 "), resol: Hitachi changes into industry (strain) system, " Hitanol#1501 "
(4) thermally expandable graphite: Air Water Chemical (strain) system, " SS-3 " (220 ℃ of the beginning temperature that expands)
(5) aluminum phosphite: peaceful chemical industry (strain), " APA-100 "
(6) inorganic filler: clay; (strain) group horse feldspar bed of state is gone into mine system, " FA-80 ", carbon black; Rising sun Carbon (strain) system, " #80 ", aluminium hydroxide; Clear and electrician's (strain) makes " Hydilite H31 "
(7) vulcanizing agent: powder sulphur; Thin well chemical industry (strain) system
(8) vulcanization accelerator: dimethyl dithiocarbamate zinc; Imperial palace emerging (strain) system, " Nocceler PZ ", di-n-butyl two thiocarbamate zinc; Imperial palace emerging (strain) system, " Nocceler BZ ", normal-butyl formaldehyde aniline; Imperial palace emerging (strain) system, " Nocceler8N "
In embodiment 1~6 and the comparative example 1~9, estimated following characteristic.The measuring method of each characteristic is expressed as follows.And, in test film, used the zonal fire-resistant covering material that the flame resistance rubber composition is processed as vertical 25mm * horizontal 100mm * thick 2mm.
(1) thermal expansion multiplying power: measured the expansion multiplying power test film placed 0.5 hour in remaining 300 ℃ atmosphere after.
(2) processibility: in the calendaring molding machine test film being shaped, the test film that can be shaped is evaluated as " good " no problemly, will bad order take place or can't realize that the test film of stable shaping is evaluated as " not good ".
(3) shape stability: utilize the visual shape of having estimated the test film after the thermal expansion multiplying power mensuration that contact with finger.To avalanche not take place and be evaluated as " good " with the finger contact yet test film of not avalanche, will be evaluated as " not good " because of the test film of finger contact avalanche immediately or avalanche.
(4) penetration degree:, under 25 ℃ of load 100g, temperature, measure according to JIS-K2207.
(5) sulphidity: utilize the method for putting down in writing among the JIS-K6300, measured moment with キ ュ ラ ス ト メ one , one III type (JSRTrading corporate system).Sulphidity (%)=(MX-ML)/(MM-ML) * 100 (MX is the moment values of having passed through the material during certain, and ML is for measuring the minimum value of the moment in the curve, and MM is for measuring the maximum value of the moment in the curve)
(6) the T mould is peeled off bonding strength: according to the bonding strength of having peeled off the bonding strength determination of test method of JIS K6854.To size be on the SUS plate of the 150mm * thick 2mm of vertical 25mm * laterally folder across test film hand roller crimping.After attaching, reach soon placed 4 months in 50 ℃ of baking ovens after, peeling rate is made as 50mm/min, carried out the T mould and peeled off bonding strength test.
The cooperation ratio that table 1 and table 2 expression change aqueous rubber, isoprene-isobutylene rubber, tackiness agent, thermally expandable graphite, aluminum phosphite, inorganic filler, vulcanizing agent, vulcanization accelerator forms each characteristic of the test film of shape.It is 3 liters pressurization kneader (machine name: the DS3-10MWB-S type) that test film is to use the mixing capacity of the oriyama of M Co., Ltd. system, under 80 ℃ with 40 rev/mins rotating speed with mixing 5 minutes of aqueous rubber, isoprene-isobutylene rubber, tackiness agent, thermally expandable graphite, aluminum phosphite, inorganic filler, add vulcanizing agent and vulcanization accelerator, after mixing 5 minutes, using the calendaring molding machine under 80 ℃, to make test film with identical rotating speed under 100 ℃ again.
As shown in table 1, embodiments of the invention 1~6 also possess good shape stability when keeping enough thermal expansion multiplying power and good processibility.In addition, penetration degree is 30~65, and soon T mould is peeled off bonding strength more than 5N/25mm after the attaching, possesses ideal flexibility and enough cementabilities.
In addition, in the evaluation of virgin sulfur voltinism, the sulphidity of embodiment 1~6 after under 50 ℃ the atmosphere 4 months is all more than 70%, and penetration degree reduces more than 10%.The reduced rate of concrete penetration degree reaches 13~17% in embodiment 1~3 and 6, reach about 25% in embodiment 4 and 5.Like this, the T mould is peeled off bonding strength and is become 39~55N/25mm about soon 5N/25mm after attach among the embodiment 1~6, is increased to about 8 times.These numbers illustrated, the fire-resistant covering material of embodiment 1~6 possess the stationarity after suitable vulcanization rate and the enough sulfuration.
The comparative example that provides in the following his-and-hers watches 2 describes.
Comparative example 1 is not owing to cooperate tackiness agent, thermally expandable graphite, aluminum phosphite, inorganic filler, so cementability deficiency (the T mould is peeled off bonding strength, with reference to after attaching soon), the shortcoming thermal expansivity, and it is bad that shape stability also becomes.
Comparative example 2 is not owing to cooperate tackiness agent, so cementability becomes not enough.
Therefore comparative example 3 is short of thermal expansivity owing to do not cooperate expansile graphite.
Comparative example 4 is made as 20 mass parts with respect to basic rubber constituent 100 mass parts with aluminum phosphite.Under this situation, it is bad that shape stability becomes.
Therefore comparative example 5 is short of the virgin sulfur voltinism owing to do not cooperate vulcanizing agent, vulcanization accelerator.As the evaluation of concrete virgin sulfur voltinism, even after under 50 ℃ of atmosphere 4 months, the rising (the T mould is peeled off bonding strength, with reference to reaching 50 ℃ after attaching soon after following 4 months) of bonding strength is not seen in yet sulfuration.
Comparative example 6 is engaged to 110 mass parts with respect to basic rubber constituent 100 mass parts with thermally expandable graphite.Under this situation, though the thermal expansion multiplying power improves, it is bad that shape stability becomes.
Comparative example 7 is with respect to aqueous rubber being made as 60 mass parts, isoprene-isobutylene rubber being made as basic rubber constituent 100 mass parts of 40 mass parts, aluminum phosphite is engaged to 190 mass parts, in addition inorganic filler is engaged to 180 mass parts (aluminium hydroxide, sooty add up to).Under this situation, it is bad that processibility becomes, and penetration degree becomes 80, and it is excessive that flexibility becomes.
Comparative example 8 has cooperated 7 mass parts vulcanizing agents with respect to basic rubber constituent 100 mass parts, also vulcanization accelerator is engaged to 10.5 mass parts (total of Nocceler PZ, BZ, 8N).Under this situation, it is bad that processibility becomes.This be because, natural vulcanization speed becomes too fast, vulcanization reaction carries out in mixing forming process, has lost flexibility.
[table 1]
Unit Embodiment
1 2 3 4 5 6
Cooperate Aqueous rubber polybutene H-300 Mass parts 40 40 50 30 40 40
Isoprene-isobutylene rubber Butyl268 Mass parts 60 60 50 70 60 60
Tackiness agent YSResin PX-100 Hitanol#1501 Mass parts 15 20 15 20 15 20 15 20 15 20 15 20
Thermally expandable graphite SS-3 Mass parts 30 60 30 30 30 40
Aluminum phosphite APA-100 Mass parts 130 130 130 130 130 50
Inorganic filler FA-80 Hydilite H31 Carbon#80 Mass parts - 120 5 - 120 5 - 150 5 70 - 5 - 140 5 - 60 10
Vulcanizing agent sulphur Mass parts 1 1 1 1 2 1
Vulcanization accelerator Nocceler-PZ Nocceler-BZ Nocceler-8N Mass parts 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 1 1 1 0.5 0.5 0.5
Characteristic The thermal expansion multiplying power Doubly 5 7 5 5 5 5
Processibility - Well Well Well Well Well Well
Shape stability - Well Well Well Well Well Well
Penetration degree 1/10mm 40 37 50 34 40 42
50 ℃ through the penetration degree after 120 days 1/10mm 35 32 42 25 30 35
50 ℃ through the sulphidity after 120 days 80 80 80 80 90 80
After the T mould is peeled off bonding strength and attached 50 ℃ after 4 months soon N/25mm 5.5 43 5.1 40 5.8 45 5.0 39 5.5 55 5.4 45
[table 2]
Unit Comparative example
1 2 3 4 5 6 7 8
Cooperate Aqueous rubber polybutene H-300 Mass parts 40 40 40 40 40 40 60 40
Isoprene-isobutylene rubber Butyl268 Mass parts 60 60 60 60 60 60 40 60
Tackiness agent YSResin PX-100 Hitanol#1501 Mass parts - - 15 20 15 20 15 20 15 20 15 20 15 20
Thermally expandable graphite SS-3 Mass parts - 30 - 30 30 110 30 30
Aluminum phosphite APA-100 Mass parts - 130 130 20 130 130 190 130
Inorganic filler FA-80 Hydilite H31 Carbon#80 Mass parts - - - - - - - 120 5 - 120 5 - 120 5 - 120 5 - 170 10 - 120 5
Vulcanizing agent sulphur Mass parts 1 1 1 1 - 1 1 7
Vulcanization accelerator Nocceler-PZ Nocceler-BZ Nocceler-8N Mass parts 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 - - - 0.5 0.5 0.5 0.5 0.5 0.5 3.5 3.5 3.5
Characteristic The thermal expansion multiplying power Doubly - 5 - 6 5 9 5 5
Processibility - Well Well Well Well Well Well Not good Not good
Shape stability - Not good Well Well Not good Well Not good Well Well
Penetration degree 1/10mm 160 100 40 47 37 40 80 40
50 ℃ through the penetration degree after 120 days 1/10mm 150 90 33 41 37 35 64 19
50 ℃ through the sulphidity after 120 days 80 80 80 80 - 80 80 90
After the T mould is peeled off bonding strength and is attached after 4 months soon N/25mm 3.1 29.2 2.5 24.5 5.6 44 5.5 43 5 5 5.3 42 4.8 45 5.6 50
Table 3 expression change the mixing operation (5 minutes) of having added behind vulcanizing agent and the vulcanization accelerator and be shaped with the calendaring molding machine in temperature and must each characteristic of test film.Though the cooperation ratio of embodiment 1 and comparative example 9 aqueous rubber, isoprene-isobutylene rubber, tackiness agent, thermally expandable graphite, aluminum phosphite, inorganic filler, vulcanizing agent, vulcanization accelerator is identical, but the temperature of mixing operation and forming process is respectively 100 ℃, 80 ℃ among the embodiment 1, different with it, all be set at 130 ℃ in the comparative example 9.
In the comparative example 1, by with the temperature maintenance of mixing operation forming process below 100 ℃, the sulphidity of test film can be suppressed be 3%, however in the comparative example 9, be set at up to 130 ℃ by the temperature with mixing forming process, the sulfuration of test film proceeds to 12%.In the comparative example 9, because of sulfuration like this aggravation carry out, thereby penetration degree is reduced to 58, the forfeiture flexibility causes the reduction of cementability.
[table 3]
Unit Embodiment Comparative example
1 9
Cooperate Aqueous rubber polybutene H-300 Mass parts 40 40
Isoprene-isobutylene rubber Butyl268 Mass parts 60 60
Tackiness agent YSResin PX-100 Hitanol#1501 Mass parts 15 20 15 20
Thermally expandable graphite SS-3 Mass parts 30 30
Aluminum phosphite APA-100 Mass parts 130 130
Inorganic filler FA-80 Hydilite H31 Carbon#80 Mass parts - 120 5 - 120 5
Vulcanizing agent sulphur Mass parts 1 1
Vulcanization accelerator Nocceler-Pz Nocceler-BZ Nocceler-8N Mass parts 0.5 0.5 0.5 0.5 0.5 0.5
Mixing forming temperature 100·80 130·130
Characteristic Shaping postcure degree 3 12
Penetration degree 1/10mm 80 58
After the T mould is peeled off bonding strength and is attached soon N/25mm 5.5 2.3
At last, use is made as the test film of the cooperation ratio identical with embodiment 1~6, the other side's column type Steel Skeleton carries out the construction operation achievement of fire-resistant covering in handling and describes.
Test film is processed as the band shape of 1500mm * thick 2mm of vertical 1000mm * laterally, one side is covered with aluminium foil, opposite one side (bonding plane) is attached on the square column shaped steel skeleton (wide 300mm * dark 300mm * high 1500mm, iron plate thickness 6mm).
No matter at which kind of cooperate in the test film of ratio, do not need other reinforcement to fix, test film is bonded, remain on Steel Skeleton surface, the situation of not peeling off.
Hence one can see that, different with fire prevention in the past with expanding material, in the fire-resistant covering material of the present invention, can confirm need after attaching, not utilize nail, pin, bolt etc. to strengthen fixedly surfacings such as non-woven fabrics, wire netting, stupalith, can shorten the engineering time significantly from the outside.In addition also as can be known, owing to not needing to use caking agent, therefore the foul smell that is not caused by caking agent owing to do not need carrying necessary instrument class in reinforcement is fixing, therefore can alleviate constructor's burden.
Flame resistance rubber composition of the present invention, the fire-resistant covering material that is made of this flame resistance rubber composition and the fire-resistant covering treatment process of having used this fire-resistant covering material, the fire-resistant covering that can be used for Steel Skeleton etc. is handled.In addition, be wound on seam sealer by fire prevention and insert on the power cable in the peristome as the gap between fireproof brickwork and the power cable etc., then when preventing fire spread or buildings collapse very useful.

Claims (9)

1. unvulcanized flame resistance rubber composition, wherein in described unvulcanized flame resistance rubber composition, with respect to basic rubber constituent 100 mass parts that constitute by aqueous rubber 30~50 mass parts, isoprene-isobutylene rubber 50~70 mass parts, contain tackiness agent 10~60 mass parts, thermally expandable graphite 10~100 mass parts, aluminum phosphite 50~170 mass parts, inorganic filler 50~170 mass parts, vulcanizing agent 0.1~10 mass parts, vulcanization accelerator 0.1~10 mass parts, and this flame resistance rubber composition is used at 60~100 ℃ mixing down.
2. flame resistance rubber composition according to claim 1 is characterized in that, after following mixing treatment process, penetration degree is 30~65, and sulphidity is below 5%,
Described mixing treatment process is to use two rotors formula kneading device, at 80 ℃, with 40 rev/mins rotating speed mixing 5 minutes, adds described vulcanizing agent and described vulcanization accelerator, then under 100 ℃ with the mixing 5 minutes treatment process of described rotating speed.
3. flame resistance rubber composition according to claim 1 and 2 is characterized in that, after the described mixing treatment process, under 50 ℃ of atmosphere through 120 days after, sulphidity is more than 70%.
4. fire-resistant covering material that is shaped by any described flame resistance rubber composition in the claim 1 to 3.
5. fire-resistant covering material according to claim 4 is characterized in that, has banded or laminar shape.
6. the manufacture method of a fire-resistant covering material, wherein, in claim 1~3 any described flame resistance rubber composition 60~100 ℃ mixing down after, form.
7. the manufacture method of the described fire-resistant covering material of claim 6 is characterized in that, forming temperature is lower than melting temperature.
8. fire-resistant covering treatment process of having used claim 4 or 5 described fire-resistant covering materials.
9. fire-resistant covering treatment process according to claim 8, it is characterized in that, after substrate surface is bonding, utilize the natural vulcanization of this fire-resistant covering material to make it immobilization on substrate surface at the bounding force that described fire-resistant covering material is utilized this fire-resistant covering material then.
CN2007101811812A 2006-10-12 2007-10-12 Fire-resistant rubber composition, fire-resistant covering material composed of the composition and fire-resistant covering processing method using the same Active CN101161715B (en)

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